Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
  • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/002—Aftershave preparations
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/32—Polymerisation in water-in-oil emulsions
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/54—Polymers characterized by specific structures/properties
  • A61K2800/542—Polymers characterized by specific structures/properties characterized by the charge
  • A61K2800/5424—Polymers characterized by specific structures/properties characterized by the charge anionic
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
  • A61Q1/14—Preparations for removing make-up
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/004—Aftersun preparations
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/005—Preparations for sensitive skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/007—Preparations for dry skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/008—Preparations for oily skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/04—Preparations for care of the skin for chemically tanning the skin
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/06—Preparations for care of the skin for countering cellulitis

Definitions

• the present application relates to thickening water-in-oil latices, to a process for their preparation and to their application as thickeners and/or emulsifiers for skincare products and haircare products or for the manufacture of cosmetic, dermopharmaceutical or pharmaceutical preparations.
• Synthetic polymers in powder form mainly polyacrylic acids, are also widely used but have the drawback of requiring neutralization when they are used, since they only develop their viscosity from a pH >6.5 and they are often difficult to dissolve.
• Synthetic thickening polymers in the form of an inverted latex that is to say one in which the continuous phase is an oil, are also known. These latices dissolve extremely quickly; the polymers contained in these inverted latices are usually acrylamide/alkali metal acrylate copolymers or acrylamide/sodium 2-acrylamido-2-methylpropane-sulphonate co-polymers; they are already neutralized and when they are dissolved in water, for example to a concentration of 1%, it is observed that the pH is generally above 6.
• acrylamide/sodium acrylate copolymers do not develop any appreciable thickening properties when the pH is lowered below 6; on the other hand, the acrylamide/sodium 2-acrylamido-2-methylpropane-sulphonate copolymers described in EP 0,503,853 retain an appreciable thickening capacity even at pH 4.
• the Applicant has thus been concerned with the synthesis and development of polymers that thicken, even at acidic pH, in the form of an inverted latex, without using monoacrylamide.
• compositions comprising an oil phase, an aqueous phase, at least one emulsifier of water-in-oil (W/O) type, at least one emulsifier of oil-in-water (O/W) type, characterized in that the composition is an inverted latex comprising from 20% to 60% by weight, and preferably from 25% to 45% by weight, of a branched or crosslinked anionic polyelectrolyte based on at least one monomer possessing a strongly acidic function, copolymerized either with at least one monomer possessing a weakly acidic function or with at least one neutral monomer.
• W/O water-in-oil
• O/W oil-in-water
• emulsifier of the water-in-oil type is understood to denote emulsifiers having an HLB value that is low enough to give water-in-oil emulsions, such as the surfactant polymers sold under the name HypermerTM or such as sorbitan extracts, for instance sorbitan monooleate sold by the company SEPPIC under the tradename Montane 80TM, or sorbitan isostearate sold by SEPPIC under the name Montane 70TM.
• emulsifier of the oil-in-water type is understood to denote emulsifiers having an HLB value that is high enough to give oil-in-water emulsions, such as ethoxylated sorbitan esters, for instance sorbitan oleate ethoxylated with 20 mol of ethylene oxide, sold by SEPPIC under the name MONTANOX 80TM.
• branched polymer is understood to denote a non-linear polymer which has pendant chains so as to obtain, when this polymer is dissolved in water, a high degree of entangling leading to very high low-gradient viscosities.
• crosslinked polymer is understood to denote a non-linear polymer in the form of a three-dimensional network which is insoluble in water but swellable in water and thus leading to the production of a chemical gel.
• composition according to the invention can contain crosslinked units and/or branched units.
• the subject of the invention is, in particular, a composition as defined above, characterized in that the anionic polyelectrolyte is the result of a copolymerization of its precursor monomers, which is carried out at a pH below 4.
• the subject of the invention is also a composition as defined above, characterized in that 30% to 90% of the monomer units which comprise the anionic polyelectrolyte have a strongly acidic function.
• the strongly acidic function of the monomer containing it is, in particular, a sulphonic acid function or a phosphonic acid function, partially or totally salified.
• the monomer can be for instance, styrenesulfonic acid partially or totally salified. It is preferably 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulphonic acid partially or totally salified in the form of an alkali metal salt or an ammonium salt.
• the weakly acidic function of the monomer containing it is, in particular, a carboxylic acid function, and the monomer is preferably chosen from acrylic acid, methacrylic acid, itaconic acid and maleic acid.
• the neutral monomer is chosen in particular from 2-hydroxyethyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate and 2,3-dihydroxypropyl methacrylate, or an ethoxylated derivative, with a molecular weight between 400 and 1000, of each of these esters.
• composition comprising an oil phase, an aqueous phase, at least one emulsifier of water-in-oil (W/O) type and at least one emulsifier of oil-in-water (O/W) type, characterized in that the said composition is a reverse latex comprising from 20% to 60% by weight, and preferably from 25% to 45% by weight, of a branched or crosslinked, anionic polyelectrolyte based on partially or totally salified 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, copolymerized with 2-hydroxyethyl acrylate, more particularly, a composition as defined above, characterized in that 30% to 90%, preferably 50% to 90%, in molar proportions, of the monomer units comprised by the anionic polyelectrolyte is 2-methyl-2-[(1-oxo-2-propenyl)amino]-1
• composition as defined above, characterized in that the composition is a reverse latex comprising from 20% to 60% by weight, and preferably from 30% to 45% by weight, of a branched or crosslinked, anionic polyelectrolyte based on a 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid, which is partially or totally salified in the form of sodium salt or of ammonium salt, copolymerized with acrylic acid, partially salified in the form of the sodium salt or of ammonium salt.
• the subject of the invention is, more particularly, a composition as defined above, characterized in that the anionic polyelectrolyte is crosslinked and/or branched with a diethylenic or polyethylenic compound in a molar proportion, expressed relative to the monomers used, of from 0.005% to 1% and preferably from 0.01% to 0.2%, and more particularly from 0.01% to 0.1%, and preferably that for which the crosslinking agent and/or the branching agent is chosen from ethylene glycol dimethacrylate, sodium diallyl-oxyacetate, ethylene glycol diacrylate, diallylurea, trimethylolpropane triacrylate or methylene-bisacrylamide.
• the latex according to the invention generally contains from 2.5% to 15% by weight, and preferably from 4% to 9% by weight, of emulsifiers, among which from 20% to 50%, in particular from 25% to 40%, of the total weight of the emulsifiers present are of the water-in-oil (W/O) type and in which from 80% to 50%, in particular from 75% to 60%, of the total weight of the emulsifiers are of the oil-in-water (O/W) type.
• W/O water-in-oil
• O/W oil-in-water
• the composition as defined above is characterized in that the oil phase represents from 15% to 40%, preferably from 20% to 25%, of its total weight.
• This oil phase either consists of a commercial mineral oil containing saturated hydrocarbons such as paraffins, isoparaffins or cycloparaffins having, at room temperature, a density of between 0.7 and 0.9 and a boiling point above 180° C., such as, for example, ExxsolTM D 100 S or MarcolTM 52 sold by Exxon Chemical, isohexadecane or isododecane, or consists of a plant oil or a synthetic oil or of a mixture of several of these oils.
• a commercial mineral oil containing saturated hydrocarbons such as paraffins, isoparaffins or cycloparaffins having, at room temperature, a density of between 0.7 and 0.9 and a boiling point above 180° C.
• ExxsolTM D 100 S or MarcolTM 52 sold by Exxon Chemical
• isohexadecane or isododecane or consists of a plant oil or a synthetic oil or of a mixture of several of these oils.
• the latices contain between 20% and 50% water.
• the latices according to the invention can also contain various additives such as completing agents, transfer agents or chain-limiting agents.
• composition as defined above, characterized in that:
• an aqueous solution containing the monomers and the optional additives is emulsified in an oil phase in the presence of one or more emulsifiers of water-in-oil type,
• the polymerization reaction is initiated by introducing a free-radical initiator into the emulsion formed in a), after which the reaction is left to proceed,
• one or more emulsifiers of oil-in-water type are introduced at a temperature below 50° C.
• reaction medium obtained after step b) is concentrated by distillation before step c) is carried out.
• the polymerization reaction is initiated by a redox couple, such as the cumene hydroperoxide/sodium metabisulphite couple, at a temperature below or equal to 10° C., and is then carried out either in a virtually adiabatic manner up to a temperature above or equal to 40° C., more particularly above or equal to 50° C., or by controlling the temperature evolution.
• a redox couple such as the cumene hydroperoxide/sodium metabisulphite couple
• the starting aqueous solution is adjusted to a pH below or equal to 4 before step c) is carried out.
• the subject of the invention is also the use of the composition as defined above for preparing a cosmetic, dermo-pharmaceutical or pharmaceutical topical composition.
• a topical composition according to the invention intended to be applied to the skin or mucous membranes of humans or animals can consist of a topical emulsion comprising at least one aqueous phase and at least one oil phase.
• This topical emulsion can be of the oil-in-water type. More particularly, this topical emulsion can consist of a fluid emulsion, such as a fluid gel or milk.
• the oil phase of the topical emulsion can consist of a mixture of one or more oils.
• a topical composition according to the invention can be intended for cosmetic use or can be used to prepare a medical product intended for the treatment of mucous and skin diseases.
• the topical composition then contains an active principle which can consist, for example, of an anti-inflammatory agent, a muscle relaxant, an antifungal agent or an antibacterial agent.
• topical composition When used as a cosmetic composition intended to be applied to the skin or mucous membranes, it may or may not contain an active principle, for example a moisturizer, a tanning agent, a sunscreen, an anti-wrinkle agent, a slimming agent, an anti-radical agent, an antiacne agent or an antifungal agent.
• an active principle for example a moisturizer, a tanning agent, a sunscreen, an anti-wrinkle agent, a slimming agent, an anti-radical agent, an antiacne agent or an antifungal agent.
• a topical composition according to the invention usually contains between 0.1% and 10% by weight of the thickener defined above.
• the pH of the topical composition is preferably above or equal to 5.
• the topical composition can also contain compounds conventionally included in compositions of this type, for example fragrances, preserving agents, dyes, emollients or surfactants.
• the invention relates to the use of the novel thickener mentioned above, in accordance with the invention, to thicken and emulsify a topical composition comprising at least one aqueous phase.
• composition according to the invention is an advantageous substitute for those sold under the name SepigelTM 305 or SepigelTM 501 by the Applicant, since it also has good compatibility with the other excipients used for the preparation of formulations such as milks, lotions, creams, soaps, baths, balms, shampoos or conditioners. It can also be employed with the SepigelTM.
• composition is compatible with the concentrates described and claimed in the international publications WO 92/06778, WO 95/04592, WO 95/13863, WO 96/37285, WO 98/22207, WO 98/47610 or in FR 2,734,496, and with the surfactants described in WO 93/08204.
• the composition is particularly compatible with MontanovTM 68, MontanovTM 82, MontanovTM 202 or SepiperlTM N. It can also be used in emulsions of the type described and claimed in EP 0,629,396 and in cosmetically or physiologically acceptable aqueous dispersions with an organopolysiloxane compound chosen, for example, from those described in WO 93/05762 or in WO 93/21316.
• the composition can also be used to form cosmetically or physiologically acceptable gels that are aqueous at acidic pH, such as those described in WO 93/07856; it can also be used in combination with nonionic celluloses in order to form, for example, styling gels, such as those described in EP 0,684,024, or alternatively in combination with fatty acid esters of a sugar, in order to form compositions for treating the hair or the skin, such as those described in EP 0,603,019, or alternatively in shampoos or conditioners as described and claimed in WO 92/21316, or, lastly, in combination with an anionic homopolymer such as CarbopolTM in order to form hair-treatment products, such as those described in DE 195 23596.
• an anionic homopolymer such as CarbopolTM
• composition according to the invention is also compatible with active principles such as, for example, self-tanning agents, for instance dihydroxyacetone (DHA) or antiacne agents, and it can thus be introduced into self-tanning compositions such as those claimed in EP 0,715,845, EP 0,604,249, EP 0,576,188 or in WO 93/07902.
• self-tanning agents for instance dihydroxyacetone (DHA) or antiacne agents
• composition is also compatible with N-acylated derivatives of amino acids, which allows it to be used in soothing compositions especially for sensitive skin, such as those described or claimed in WO 92/21318, WO 94/27561 or WO 98/09611.
• the pH of the aqueous phase described above is adjusted to 3.5 and the amount of aqueous phase is made up to 682 g by adding deionized water.
• an organic phase is prepared by introducing the following ingredients successively into a stirred beaker:
• the aqueous phase is introduced gradually into the organic phase and is then subjected to vigorous mechanical stirring of ultra-turraxTM type sold by IKA.
• the emulsion obtained is then transferred into a polymerization reactor. A large amount of nitrogen is bubbled through the emulsion so as to remove the oxygen, and the resulting emulsion is cooled to about 5-6° C.
• aqueous sodium metabisulphite solution (0.2 g in 100 ml of water) is then introduced at a rate of 0.5 ml/minute. The introduction is carried out over about 60 minutes.
• the temperature in the polymerization reactor is allowed to rise to the final polymerization temperature.
• the reaction medium is then held at this temperature for about 90 minutes.
• the mixture is cooled to a temperature of about 35° C. and 50 g of sorbitan oleate ethoxylated with 20 mol of ethylene oxide are introduced slowly.
• the desired emulsion is obtained.
• the desired emulsion which has the following characteristics:
• the pH of the aqueous phase described above is adjusted to 3.5, by adding 0.7 g of 2-methyl-2-[(1-oxo-2-propenyl)amino]-1-propanesulfonic acid.
• an organic phase is prepared by introducing the following successively into a stirred beaker:
• the aqueous phase is introduced gradually into the organic phase and is then subjected to vigorous mechanical stirring with an Ultra-TurraxTM machine sold by IKA.
• the emulsion obtained characterized by a viscosity at 25° C. of 2600 mPa.s (Brookfield RVT, No. 4 spindle, speed 20), is then transferred into a polymerization reactor.
• the emulsion is subjected to bubbling with nitrogen at a substantial rate so as to remove the oxygen, and is cooled to about 5-6° C.
• the desired emulsion is obtained.
• the emulsions obtained have a very specific feel sensation at and above 1% polymer in the solution, and that this difference increases as the concentration increases; it is a very fresh feel sensation at the start, which melts completely on the skin, this feel sensation not being experienced at all with the latices of the prior art.
• composition 1 The inverted latex prepared in paragraph A] b) (composition 1) was used to prepare emulsions with different types of a polar or polar fatty substances of plant or synthetic origin.
• the cream-gels obtained in the various cases are stable and have an entirely homogeneous appearance. Their viscosity is given in the following table:
• Composition 1 thus makes it possible to disperse and stabilize the fatty phases in an aqueous medium, by simple dilution without a neutralization step being necessary.
• composition 1 a cream-gel comprising 2.5% of composition 1 and 20% of cetearyl octanoate was prepared and the viscosity was measured.
• the results are as follows:
• the viscosity (in mPa.s) of gels containing 3% of composition 1 was measured in various cosmetic solvents at several concentrations.
• Solvent 20% 40% 60% Hexylene glycol ⁇ 100,000 ⁇ 10,000 5000 Ethanol ⁇ 100,000 100,000 40,000 Dipropylene glycol ⁇ 100,000 100,000 90,000 Butylene glycol ⁇ 100,000 ⁇ 100,000 ⁇ 100,000 Propylene glycol ⁇ 100,000 ⁇ 100,000 ⁇ 100,000 Glycerol ⁇ 100,000 ⁇ 100,000 ⁇ 100,000
• the feel sensation of the emulsions obtained is very specific at and above 1% polymer in the solution and this difference increases as the concentration increases; it is a very fresh feel sensation at the start, which melts completely on the skin, this feel sensation not being experienced at all with the latices of the prior art.
• Micropearl TM M310 1.0% Compound of Example 1 5.0% Octyl isononanoate: 4.0% B Water: q.s. 100% C Sepicontrol TM A5: 4.0% Fragrance: 0.1% Sepicide TM HB: 0.3% Sepicide TM CI: 0.2% D Capigel TM 98: 0.5% Water: 10%
• MontanovTM 68 cetearyl glucoside is a self-emulsifying composition as described in WO 92/06778, sold by the company SEPPIC.
• MicropearlTM M100 is an ultra-fine powder with a very soft feel sensation and a matt effect, sold by the company Matsumo.
• SepicideTM CI imidazolinurea
• SEPPIC Stamate Phosphide
• PemulenTM TR is an acrylic polymer sold by Goodrich.
• SimulsolTM 165 is self-emulsifying glyceryl stearate, sold by the company SEPPIC.
• LanolTM 1688 is a non-greasy emollient ester sold by the company SEPPIC.
• LanolTM 14M and LanolTM S are consistency factors sold by the company SEPPIC.
• Sepicide TM HB which is a mixture of phenoxyethanol, methylparaben, ethylparaben, propylparaben and butylparaben, is a preserving agent sold by the company SEPPIC.
• MonteineTM CA is a moisturizer sold by the company SEPPIC.
• SchercemolTM OP is a non-greasy emollient ester.
• LanolTM P is a stabilizing additive sold by the company SEPPIC.
• ParsolTM MCX is octyl para-methoxycinnamate, sold by the company Givaudan.
• SepiperlTM N is a pearlescent agent, sold by the company SEPPIC, based on a mixture of alkylpolyglucosides such as those described in WO 95/13863.
• MicropearlTM SQL is a mixture of microparticles containing squalane, which is released under the action of massaging; it is sold by the company Matsumo.
• LanolTM 99 is isononyl isononanoate, sold by the company SEPPIC.
• LanolTM 37T is glyceryl triheptanoate, sold by the company SEPPIC.
• SolagumTM L is a carrageenan sold by the company SEPPIC.
• MarcolTM 82 is a liquid paraffin sold by the company ESSO.
• LanolTM 84D is dioctyl malate, sold by the company SEPPIC.
• ParsolTM NOX is a sunscreen sold by the company Givaudan.
• EusolexTM 4360 is a sunscreen sold by the company Merck.
• Dow CorningTM 245 Fluid is cyclomethicone, sold by the company Dow Corning.
• LipacideTM PVB is a palmitoylated wheat protein hydrolysate sold by the company SEPPIC.
• MicropearlTM LM is a mixture of squalane, poly(methyl methacrylate) and menthol, sold by the company SEPPIC.
• SepicontrolTM A5 is a mixture of capryloylglycine, sarcosine and extract of Cinnamon zylanicum, sold by the company SEPPIC, such as those described in International patent application PCT/FR 98/01313 filed on Jun. 23, 1998.
• CapigelTM 98 is an acrylate copolymer sold by the company SEPPIC.
• LanolTM 2681 is a coconut caprylate/caprate mixture sold by the company SEPPIC.
• MontanovTM 202 is an APG/fatty alcohol composition as described in W09 98/47610, sold by the company SEPPIC.

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• Health & Medical Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Veterinary Medicine (AREA)
• Public Health (AREA)
• General Health & Medical Sciences (AREA)
• Chemical & Material Sciences (AREA)
• Animal Behavior & Ethology (AREA)
• Dermatology (AREA)
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• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
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• 1999
  • 1999-01-14 EP EP03292022A patent/EP1369435B1/fr not_active Expired - Lifetime
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  • 1999-01-14 EP EP99900919A patent/EP1047716B1/fr not_active Revoked
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  • 1999-01-14 ES ES03292022T patent/ES2269947T3/es not_active Expired - Lifetime
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• 2009
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